Waxy crayon or ink-like diazotype developer composition comprising heat transferrable azo coupler and transfer promotor

ABSTRACT

A process for diazo-type multicolor reproduction according to which it is possible to obtain multi-colored copies in which portions corresponding to predetermined portions of an original area colored selectively in different hues without substantial mingling of colors, by conducting the heat transfer at relatively low temperatures (for instance, at 60* - 80*C.), and a color former to be used in such process, which comprises a thermosublimative coupler and a thermosublimative, organic, solid transfer promotor having no coupling property in itself.

United States Patent Nihyakumen et al.

[ Sept. 23, 1975 Mita Industrial Company, Ltd., Osaka, Japan Filed: Jan.17, 1974 Appl. No.: 434,139

Related U.S. Application Data Continuation of Ser. No. 139,442, May 3,1971, abandoned.

Assignee:

Foreign Application Priority Data May 1, 1970 Japan 45-36851 U.S. Cl96/49; 96/75; 96/91 R; 106/19; 117/368; 117/369; 250/317; 250/318 Int.Cl. G03C 5/34 Field of Search 96/49.75, 91 R; 117/368,

References Cited UNITED STATES PATENTS 4/1957 Kosar 96/49 3,162,76312/1964 Huett et a1 250/318 3,169,067 2/1965 Benbrook et a1. 96/493,169,069 2/1965 Berman et al. 96/49 X 3,364,858 l/1968 Kojima et a1.250/318 3,418,468 12/1968 Marx ct al. 250/318 3,454,764 7/1969 Collier96/49 X 3,486,900 12/1969 Tsunoda et a1. 96/49 X 3,502,871 3/1970 Marxet al. 250/318 3,715,213 2/1973 Nihyakumen ct 96/49 3,725,066 4/1973Nihyakumen et a1 96/49 FOREIGN PATENTS OR APPLICATIONS 895,249 5/1962United Kingdom 96/91 R 1,000,151 8/1965 United Kingdom 96/91 R PrimaryExaminer--Charles L. Bowers, Jr. Attorney, Agent, or FirmSherman &Shalloway [57] ABSTRACT A process for diazo-type multicolor reproductionaccording to which it is possible to obtain multi-colored copies inwhich portions corresponding to predetermined portions of an originalarea colored selectively in different hues without substantial minglingof colors, by conducting the heat transfer at relatively lowtemperatures (for instance, at60 80C.), and a color former to be used insuch process, which comprises a thermosublimative coupler and athermosub- -1imative, organic, solid transfer promotor having nocoupling property in itself.

19 Claims, 2 Drawing Figures US Patent Sept. 23,1975 3,907,567

F/ g. F g. 2

ORIGINAL I 2 3 I 2 3 i loRIeImAwigI PREPARATION OF ORIGINAL FORMULTICOLOR DEVELOPMENT SHEETFOR :1

COUPLER ESG gEE E 2' 3 LIGHT SOURCE LIGHT HEAT.

LIGHT EXPOSURE I I 2' HEAT H PI-IO'I'gSENSITIV II I2 l3 WAXY CRAYON ORINK-LIKE DIAZOTYPE DEVELOPER COMPOSITION COMPRISING HEAT TRANSFERRABLEAZO COUPLER AND TRANSFER PROMOTOR This is a continuation of applicationSer. No. 139,442, filed May 3, 1971, now abandoned.

This invention relates to a process for diazo-type multi-colorreproduction and to a color former to be used in such process. Moreparticularly, this invention relates to a process for the diazo-typemulticolor reproduction according to which it is possible to obtainmulti-colored copies in which portions corresponding to predeterminedportions of an original are colored selectively in different hueswithout substantial mingling of colors, by conducting the heat transferat relatively low temperatures (for instance, at 60 80C.), and to acolor former to be used in such process.

A process for the diazo-type multi-color reproduction has beenpreviously proposed based on the discovery that predetermined portionsof an original can be reproduced into different hues regardless ofdifference or similarlity of the light transmission in the original, byconducting the steps of (A) exposing to light a diazotype photosensitivematerial containing at least one diazonium salt (which will be referredto as diazonium salt and (B) heating a layer of at least onethermovolatile or thermosublimative coupler (which will be referred toas coupler (11)") disposed in face-toface contact with such diazo-typephotosensitive material at a portion corresponding to a predeterminedportion of the original to be colored in a different hue, the stepsbeing carried out coincidentally or in an order of (A) to (B) or (B) to(A), and then developing the lightexposed photosensitive material in thepresence of a coupler having a lower coupling rate under developingconditions (which will be referred as coupler (17)) than thethermovolatile or thermosublimative coupler (a). In this diazo-typemulticolor reproduction process, a thermovolatile or thermosublimativecoupler is combined with the back face of an original at one or moreportions predetermined to be colored in a different hue. Thethermovolatile coupler in the form of, for instance, an ink-like or waxycoloring composition is combined with the back face of the original bycoating or transferring. Most of thermovolatile and thermosublimativecouplers have relatively high volatilizing or sublimating temperatures,and therefore, the heat transfer must be conducted at temperaturesexceeding 100C. The high heat transfer temperature results in l thefollowing disadvantages. Namely, the life of a copy ing machine isextremely shortened and its structure is inevitably complicated.Further, the high heat transfer temperature causes various operationaldifficulties. Still further, when'multi-eolored copies are obtained byemploying two or more thermovolatile or thermosublimative couplersdiffering in their volatilizing or sublimating temperature, it isdifficult to determine the heat transfer temperature. More specifically,when the heat transfer temperature is determined depending on a couplerhaving a lower volatilizing or sublimating temperature, the amount ofthe coupler having a higher volatilizing or sublimating temperaturetransferred is very low and copies of a high color contrast cannot beobtained, whereas if the heat transfer temperature is determineddepending on the coupler ofa higher vola tilizing or sublimatingtemperature, great excess of the coupler of a lower volatilizing orsublimating temperature is transferred by one transfer treatment. withthe result that the transfer layer is consumed by conducting the heattransfer only several times and the number of copies is extremelylowered.

Further research on the above-mentioned diazo-type multicolorreproduction process has been conducted with a view to overcoming thesedefects, and it has now been found that when a certain solid substancehaving no coupling property in itself is incorporated into thethermovolatile or thermosublimative coupler (a). the transfer of thecoupler (a) to a diazo-type photosensitive material can be effected at arelatively low temperature very easily and even if two or more couplers(a) are used, heat transfer temperatures and the amounts of the couplerstransferred can be almost approximated. Based on this finding, thepresent invention has been developed.

Accordingly, the primary object of this invention is to provide adiazo-type multicolor reproduction process according to which the heattransfer of one or more couplers to a diazo-type photosensitive materialcan be effected ata relatively low temperature, and to provide a colorformer for use in conducting such process.

Another object of this invention is to provide a diazotype multicolorreproduction process according to which two or more couplers to becombined with a diazotype photosensitive material can be heattransferredwith almost equal amounts at approximating temperatures, whereby manycopies can be obtained from one original with the heat transfer layerformed thereon, while conducting the heat transfer at relatively lowtemperatures, and to provide a color former to be used in such process.

In accordance with this invention. a color former for use in thediazo-type multicolor reproduction is provided, which comprises athermovolatile or thermosublimative coupler, and a thermosublimative,organic, solid transfer promotor having no coupling property in itself.The above objects of this invention can be attained by the useof suchcolor former.

In accordance with this invention, an improvement of the above-mentioneddiazo-type multicolor reproduction process previously proposed, isprovided wherein a color former comprising a thermovolatile orthermosublimative coupler, and a thermosublimative, organic. solidtransfer promotor having no coupling property in itself is usedas thecoupler (a).

In this invention it is essential that the thermosublimative, organic,solid, transfer promoter should not possess any coupling property initself. As such transfer promotor any organic compound that exhibits ahigh sublimating property at temperatures exceeding room temperature,especially at temperatures exceeding 60C. and has a melting point above60C., preferably above C. can be used The transfer promoter may bechosen from naphthalene, naphthalene derivatives. terpene compounds,halogenated benzenes and other organic solid sublimative compounds.Typical examples of such transfer promotor are as follows:

Naphthalene d-Camphor Menthol Camphene Benzoie acid Maleic anhydridePhthalic anhydride Oxalic acid Fomic acid Anthranilic acid Ethylboricacid Phenylhydrazine hydrochloride p-Hydroxyphenyl acetic acid AtropineZ-Aminoquinoline a-Chloroacrylic acid o-Chlorobenzoic acid p-Dichlorobenze ne Chlorofumaric acid Diacetone-D-glucose 1,4 Cycl'ohexadione2.6-Dichlorobenzoic acid Di-a-naphthyl ketone N,N-diphenyl acetamide I2,4-Dimethyl-3-furan-carboxylic acid Dimethylphosphinic acidCinnamylideneacetic acid Tartronie acid Thiourethane2,3,4.5-Tetramethylpyrrol Triiodobenzene a-Naphthyl ketone1,8-Naphthylene diamine Nitrobenzonitrile Hydrochelidonic acid IPyridine carboxylic acid Pyrene Phenanthrene Phenylpropiolic acid3-Furancarboxylic acid o-Benzylbenzoie acid Bornane Meconine Mesitylenicacid 5-Methyl2-furancarboxylic acid Lapachol It 'is essential that amongthe thermovolatile or thermosublimative coupler (a) to be used in thecolor former of this invention.a coupler (h) anda diazonium salt (0) thefollowing relations should be established in conducting the multicolorreproduction according to this invention: 7

l. Thermovolatile or .thermosublimative coupler (a) has a highercoupling rate under developing conditions than coupler (h). 7

ll. Dyestuff (h)-(c), dyestuff(a)-(c), dycstuff(a')-(( formed at thedevelopment have hues different from one another.

Any coupler that can be volatilized or sublimated I under heatingconditions may be used as the ther-" movolatile or thermosublimativecoupler (a) in this invention. As such coupler (a) phenol derivatives,hydroxynaphthalene derivatives. aniline derivatives and active methylenegroup-containing compounds may be mentioned. In view of facilitation ofthe heat transfer operation it is preferred that these derivatives donot contain soluble groups such as a sulfonic acid group.

Examples of these derivatives usable as coupler (a) are as follows:

Phenol Derivatives Phenol Pyrocatechol Resorcin Phloroglucino-Hydroxybenzalcohol Resorcin monoglycol ether Resorcin diglycol etherHydrotoluquinone Pyrogallol S-Hydroxy-isophthalic acidPyrogallol-4-carboxylic acid Vanillin Isovanillic acid Vanillic acid2-l-lyclroxy-terephthalic acid Z-Hydroxy-p-toluylic acid3-Hydroxy-p-toluylic acid 5-Hydroxy-o-toluylic acid 6-Hydroxy-m-toluylicacid Para-Hydroxyphenylacetic acid Para-hydroxybenzaldehydeOrtho-hydroxybenzoic acid Ortho-hydroxybenzyl alcohol4,4-Dihydroxybiphenol 3,5-Dichloro-salicylic acid5-Chloro-2-r1itrophenol 2,5-Dihydroxyacetophenone 2,5-Dinitrophenol2,4-dinitrophenol 2,4-Dinitroresorcin 4,6-Dibromo-2-nitrophenol2.5-Dimethyl hydroquinone Aniline Derivatives Meta-aminobenzoic acidDimethyl-meta-amirio-phenol I Z-Amino-p-cresol Ortho-aminophenolMeta-aminophenol Para-aminophenol Para-chloroaniline 3.4-DiaminotolueneActive Methylene Group-Containing Compounds I -Phenyl-3-methylpyrazolone (5) l-Phenyl-3-carboxypyrazolone Acetoacctic acidanilide Acetoacetic-o-chloroanilide Hydroxynaphthalene Derivatives2,3-Dihydroxynaphthalene B-Naphthol q-Naphthol l,6 -Dihydroxynaphthalene8-Amirio-2'naphthol 2,6-Dihydroxynaphthalene 2,7 DihydroxynaphthaleneS-Hydroxy-l-naphthonic acid 2,2-dihydroxy-l,1"-binaphthyl4,4'-dihydroxy-l .l '-binaphthyl 3-Carboxy2naphthol As coupler (b) to beused in combination with the thermovolatile or thermosublimative couple(a) for conducting the multicolor reproduction with use of the colorformer of this invention. any coupler that has a lower coupling ratewith the diazonium salt (0) under the developing conditions than therate of coupling of the thermovolatile -or the'rmosublimative coupler(a) contained in the color former with the diazonium salt can be used.When a plurality of thermovolatile or thermosublimative couplers (a) areused. the coupling rate of the coupler (h) should be lower than that ofany of couplers (a). Selection of couplers (a) and (h) meeting the aboverequirement may be easily performed by those skilled in the art based onsimple experiments.

Couplers having a relatively lower coupling rate may be selected amongcouplers recited above with respect to the thermovolatile orthermosublimative couplers (a) and be used as the coupler (b). Inaddition. the following may be used as coupler b) in this invention.

Phenol Derivatives 2.5.6-Trimethylphenol Z-Hydroxymethylphenol B42-hydroxyphenyl)-propionic acid Z-(e-Phenylaminomethyl)-phenolB44-Methyl-2-hydroxyphenyl)-glutaric acid2,5-Dimethyl-6-(N-dimethylaminomethyl)-phenol l.3-Dimethyl ether ofpyrogallol a-Resorcylic acid ethanolamine B-Resorcylic acidN-Lauryl-p-aminophenol N-Acyl-m-aminophenol Meta-hydroxy-acetoanilideOrtho-N-hydroxyphenyl-monoguanidine Para-N-hydroxyphenyl-biguanidine2,5-Dimethyl-4-morpholinomethyl phenol2-Methyl-5-isopropyl-m0rpholinomethyl phenol4-Morpholinomethylresorcinol monomethyl ether 3,3',5 Trihydroxydiphenyl3,3',5,5'-Tetrahydroxydiphenyl 2,2',4,4'-Tetrahydroxydiphenyl2,4,4-Trihydroxydiphenyl-2-sulfonic acid 2,4 6,3,5'-Pentahydroxydiphenyl2,2,4,4-Tetrahydroxydiphenyl sulfide Naphthols23-Dihydroxynaphthalene-o-sulfonic acid 2-Naphthol-3,6-disulfonic acid2,7-Dihydroxynaphthalene-3-sulfonic acid 28-Dihydroxynaphthalene-o-sulfonic acidl,8-Dihydroxynaphthalene-8-sulfonic acid l,8-Aminonaphthol-5-sulfonicacid 2.7-Dihydroxynaphthalene-3,6-disulfonic acidl.8-Benzoylaminonaphthol-Z-sulfonic acidl.8-Dihydroxynaphthalene-o-sulfonic acid2Hydroxy-3-naphthionic-N-B-hydroxyethyl amide B-Hydroxynaphthionic acidaminoethylamine Z-Hydroxy-3-naphthionic-N,N-bis-,B-hydroxy ether amideS-Hydroxy-Z-naphthionic-hydroxyethyl amide l-( N-Carboethoxymethylamino)8-naphthol-4- sulfonic acid v 5-( Para-nitro )-benzamidol-naphtholl-Hydroxynaphthyl-7-phenyl-guanidine Z-Hydroxynaphthyl-8-biguanidinel-Naphthol-3-(N-B-hydroxyethyl)-sulfonie amidel-Naphthol-3-(N-o-methoxyphenyl)-sulfonic amide Bis-t5-hydroxy-7-sulfo-naphthyl( 2 ]-amine N.N-Bis[l-hydroxy-3-sulfo-naphthyl(6)]-thiourea Active MethyleneGroup-Containing Compounds Acetoacetic acid cyclohexylamide Acetoaceticacid benzylamide Cyanoacetoanilide l-( 3 '-Sulfoamide)phenyl-3-methylpyrazolene-S l-(4-CarboXy-ethylphenyl)-3-dodecyl-pyra2olone-5 S-Hydroxyl .2-naphthylimidazole2-Methyl-4-hydroxybenzimidazole 7-Methyl-4-hydroxybenzothiazole l,7-Dimethyl-4-hydroxy-benzotriazole 3-Hydroxythiophene-5-carboxylic acidl-3-4-Cyelopentatrione In conducting the diazo-type multicolorreproduction with use of the color former comprising the abovementionedthermovolatile or thermosublimative coupler (a) and thermosublimative.organic. solid transfer promotor in accordance with this invention, atfirst an original for multicolor development is formed by apply ing atleast one transparent or semi-transparent layer of a mixture of athermovolatile or thermosublimative coupler (a) and a thermosublimative.organic. solid transfer promotor onto the back surface of a transparentor semi-transparent original to be copied, in one or more predeterminedportions thereof.

The so formed original for multicolor development is over-lapped on thediazo-type photosensitive material containing at least one diazoniumsalt in a manner such that the layer of coupler (u) will confront thephotosensitive surface of the photosensitive material. and thelight-exposure and heating are effected coincidentally or successivelyin this order or the reverse order. Thus, the thermovolatilc orthermosublimative coupler (a) is heat-transferred to the predeterminedportion of the surface of the photosensitive material together with thetransfer promotor at a relatively low temperature C. and the lightresolution of the diazonium salt (0) in the photosensitive materialoccurs depending on the light transmission of the original. When the soexposed photosensitive material is developed by a method known per so,at the predetermined portion to which the coupler (a) has beenheat-transferred, the diazonium salt (c) at the non-exposed area reactsselectively and preferentially with the coupler (a) to form a dyestuff(c) (a) and at other portions the diazonium salt (c) in the non-exposedarea reacts with coupler (b) to form a dyestuff (c) (b). As a result amulticolored reproductive copy in which the predetermined portion iscolored in a hue different from that of the other portion is obtained.

The above-mentioned original for multicolor development may be prepared,for instance, by a method comprising applying a coating compositioncontaining the above-mentioned color former comprising thethermovolatile or thermosublimative coupler (a) and the transferpromotor onto the back surface of a portion predetermined to have adifferent hue, of a transparent or semi-transparent original to becopied, or by a method comprising coating or impregnating a transparentor semi-transparent substrate with a coating composition comprising thecolor former of this invention and combining the resulting sheet forheat-transferring thecoupler, with the back surface of the specificportion of the original predetermined to have a different hue in amanner such that the layer for heattransferring the coupler willconfront the photosensitive'material. l

The color former of this invention for use in the diazo-type multicolorreproduetion can be easily prepared by dispersing a thermovolatile orthermosublimative coupler (a) and a thermosublimative. organic. solidtransfer promotor in a liquid. semi-solid or solid dispersion medium.

Such color former composition will now be described by referring to someembodiments.

l. Ink-like color former composition:

'Coupler (a) 5.0 40.0 "/1 Thermosublimativc transfer promotor 5.0 30.0"/1 Coloring material 3.0 "/1 Binder 0 5.0 "/1 Dispersion assistant 0"/1 Dispersion medium balance As the dispersion medium aliphaticalcohols such as methanol, ethanol, propanol, isopropanol, isobutylalcohol and dimethyl formamide; aromatic solvents such as benzene,toluene, xylene; esters; and neutral liquids having OH groups andboiling points of 100 250C. such as water, high boiling point alcohols,e.g., n-hexyl alcohol, n-heptyl alcohol, 3-heptanol, 4-heptanol, andoctanol, and glycols, e.g., glycerine, ethylene glycol, propyleneglycol. polyethylene glycol, 1,3-butanediol, l,4-butancdiol and2,3-butanediol may be used. These liquid substances may be used singlyor in combination.

It is possible to incorporate a coloring material so as to confirm theformation of a film of the color former composition, or to use a binderfor the purpose of obtaining a good fixation of the coupler (a).

The composition of the above recipe is applied to the back surface of anoriginal in a portion predetermined to have a different hue by means ofabrush, an installed felt pen, a ball pen, a coating roller, a sprayer ora printing machine.

2. Waxy color former composition:

Coupler (a) 0.5 40.0 "/1 Thcrmosuhlimative transfer promotor 0.5 Z Wax80 5 '7( Oil 10 "/1 Coloring material 0 10 '71 The composition of theabove recipe is shaped to have a crayon stick-like form or a chalk-likeform, and

the back surface of a portion of an original predetermined to have adifferent hue is painted therewith. It is also possible to form apressure-sensitive transfer sheet by melting the above composition ordissolving it in a suitable solvent and coating the melt or solution ona substrate such as paper and plastic film. The so formedpressure-sensitive transfer sheet is overlapped on the back surface ofan original sheet. and then pressing is effected thereon by means of atypewriter or other writing means to form a heat-transferable layercomprising the coupler (a) and transfer promotor on the back surface ofan image predetermined to have a different hue.

3. Coupler-transferring sheet for treating the back surface of anoriginal:

The ink-like color former composition for treating the back surface ofan original, which was described in l or a composition obtained byincorporating a binder or an extender into such ink-like composition iscoated on a transparent or semi-transparent sheet such as paper. plasticfilm or non-woven fabric. The so formed sheet for heat-transferring thecoupler is cut into a desired size, if necessary, and then applied tothe back surface of a portion of an original predetermined to have adifferent hue. It is possible to form a pressuresensitive adhesive layeron the back surface of the coupler-transferring layer for preventing itfrom exfoliating from the original.

The so prepared original for multicolor development may be generallyused 5 to times repeatedly for the multicolor development. though theapplicable frequency of the repeated use varies depending on the amountof coupler (a) coated. the coating method, the heating method and thedeveloping method. Of course. when the heat-transferability of coupler(a) in the layer for heat-transferring the coupler is lowered, it issufficient to newly supply an additional layer for heattransferring thecoupler.

The above-mentioned color former composition in use for the multicolorreproduction is applied to the back surface of a predetermined portionof an original to be copied, and is overlapped on a photosensitivematerial in a manner such that the heat transfer layer containing thecoupler (a) and thermosublimative transfer promotor will be infacc-to-face contact with the photosensitive surface of thephotosensitive material. Then, the assembly is exposed to light andheated.

The photosensitive material containing a diazonium compound (c) may beprepared by coating a sensitizing composition comprising the diazoniumcompound (c) and optionally the coupler (12) according to need dependingon the developing method, on a substrate such as paper. plastic film.non-woven fabric and metal foil. The preparation of such photosensitivematerial will now be described by referring to same examples.

A. Sensitizing composition for dry development:

Azo coupling component (b) 0.2 5.0 "/1 Diazonium compound (c) 0.2 5.0"/1 Organic acid 0.] 5.0 "/1 Coloring matter 0.00] 0.025 Developmentpromotor l.0 l0.() "/1 Extender 0- 2.5 "/1 Solvent balance Thesensitizing composition of the above recipe is coated on a substratesuch as paper and plastic film and dried to form a photosensitive sheet.

I B. Two-component-type sensitizing composition for wet development:

Azo coupling component (b) 0.2 5. Diazonium compound (c) 0.2 5. Organicacid 0.] 5. Extender 0- 2 Stabilizer 0- 5. Coloring matter Solventbalance The sensitizing composition of the above recipe is coated on asubstrate such as paper and plastic film to form a photosensitive sheet.

C. One-component-type sensitizing composition for wet development:

Diazonium compound (c) 0.2 5.0 /1 Organic acid 0.] 5.0 "/1 Extender 92.5 "/1 Coloring matter 0,00l 0.025 Solvent balance The sensitizingcomposition of the above recipe is coated on a substrate such as paper,and dried to form a photosensitive sheet.

As the diazonium compound any diazonium com pound that can couplewiththe above-mentioned couplers (u) and (1;) under ordinary developingconditions.

CO in- OOX wherein X stands for an anion. R and R each are aliphaticgroups. and Z and Y denote groups which can be introduced into thebenzene nucleus. Specific examples of the compounds of this type are asfollows:

4-Diazo-N.N-dimethyl aniline (referred to simply as MA salt)4-Diazo-N,N-diethyl aniline (referred to simply as EA salt") 14-Diazo-N-ethyl-N-B-hydroxyethyl aniline (referred to simply as EHsalt") 4-Diazo-N,N-bis,8-hydroxyethyl aniline4-Diazo-N-methyl-N-Bhydroxyethyl aniline4-Diazo'N-ethyl-N-Bhydroxypropyl aniline Other diazonium salts ofp-phenylene diamines N.N- substituted with alkyl or hydroxy-alkylgroups:

4-Diazo-N-ethyl-N-(B-diethylamino)-ethyl aniline4-Diazo-2-chloro-N,N-diethyl aniline 4-Diazo-2'methylN.N-diethyl aniline4*Diazo-2-iodo-N,N-diethyl aniline 4'Diazo-2-trifluoromethyl-N.N-diethylaniline 4-Diazo-N-ethyl-N-benzyl aniline 4-Diazo-N-methyl-N-benzylaniline (referred to simply as methyl benzyl) Aminohydroquinoneether-type compounds of the following general formula:

xoeN.

wherein R. R and R" are alkyl or aryl groups and X stands for an anion.Specific examples of the compounds of the above type are as follows:

4-Diazo-2,5-dibutoxy-N.N-diethyl aniline 4-Diazo-2.S-diethoxy-N-benzoylaniline (referred to simply as BB salt")4-Diazo-2.5-diethoxy-N-ethyl-N-benzoyl aniline4-DiaZo-2.5-dibenzyloxy-N-benzoyl aniline4-Diazo-2-chloro-5-methoxy-N-benzoyl aniline4-Diazo-2,5-diethoxy-N-benzoyl-methyl aniline 4-Diazo-Z.S-diethoxy-Nbenzoyloxy-methyl aniline Other 4-diazo-2.5-dioxyalkyl (ordioxyaryl)-N-alkyl (or aryl) compounds and derivatives thereofAminodiphenyl compounds. aminodiphenyl amine compounds and theiranalogues of the following general formulas:

LII

wherein A is an anion. R is a divalent aryl group. R is a monovalent ordivalent aryl or alkyl group. A is a divalent group or a direct bond andexamples of the RA-R' are diarylamine (A; NH di phenyl A; direct bond).diphenyl oxide (A: O-

diaryl methane (A; -CH stilbene (A; -CH=CH-) and diaryl or dialkylsulfide (A; S).

Specific examples of the compounds of the above type are as follows:

Para-diazophenyl amine 4-diazo-2.5.4'-triethoxydiphenyl amine4Diazo-2.5.4-triethoxydiphenyl 4.4'-Bis-diazo2.2',5.5-tetrahydroxydiphenyl methane Bis-diazo-8.8'-dichloro-5.5'-dimethoxy benzidine4-Diazo-2.S-dimethoxyphenylethyl sulfide4-Diazo2.5-diethoxy-4'-methyl-diphenyl sulfide Heterocyclic aminederivatives of the following general formula:

wherein X stands for an anion. Y and Z are groups which can beintroduced into the benzene nucleus. and A is a direct bond (phenylpyrrolidine) or a divalent group such as -O (morpholine). S(thiomorpholine) and methylene (phenylpiperidine).

Specific examples of the compounds of this type are as follows:

4-Diazo-2.5-dibutoxy;N-phenyl morpholine 4-Diazo-2.S-diethoxy-N-phenylmorpholine 4-Diazo-2-methoxy-N-thio morpholine 4-Diazo-N-phenylpiperidine 4-Diazo-N-phenyl pyfrrolidine4-Diazo-2,5-di-n-butoxy-N-phenyl piperidine Other derivatives-of4-Diazo-N-phenyl heterocyclic amines.

N,N-Substituted ortho-phenylene diamine derivatives andorthoamino-phenol derivatives.

Specific examples of the compounds of this type are as follows:

2-Diazo-4-methylmercapto-N,N-dimethyl aniline2Diazo5-benzoylaniino-N.N-dimethyl aniline 2Diazo-l-naphthol-5-sulfonicacid The above-mentioned diazonium compounds may be used in the form ofa relatively stable salt with sulfuric acid or hydrochloric acid. Theymay be also used in the form of a double salt with zinc chloride. tinchloride. aluminum sulfate or the like. Further, they may be used in astate stabilized by an aryl sulfonate (in the form of a diazonium saltof an aromatic sulfonic acid). a diazosulfonate or the like.

The light exposure ofthe photosensitive material and the transfer of thecolor former of this invention to the photosensitive surface of thephotosensitive material may be effected coincidentally. For instance,when a mercury lamp is used as the light source for exposure, the heattransfer of the coupler (a) may be effected coincidentally with theexposure by the heat conveyed through a cylinder glass of the lightsourcemaintained at a relatively high temperature. Of course. the heattransfer of the coupler (a) may be also effected by'the radiationheating of an image of the original. The heat transfer of the coupler(a) may be effectively performed at a temperature above 50C.. preferably60 1009C. though a preferable heating temperature varies to some extentdepending on the type of the coupler (a) and heating time. 7 i

It is also possible to adopt a method comprising piling theabove-mentioned-original for multicolor development and thephotosensitive material, passing, the assembly through a heated rolleror an infrared radiation zone to heat the coupler layer of theoriginalat the above-mentioned temperature and to effect the heattransfer of the coupler (a). and then passing. the same through anexposure zone to effect the exposure of the photosensitive material. 3

It is also possible to adopt a methodin which the exposure and heattransfer are conducted in an order reverse to that of the above method,namely a method comprising forming an assembly of the original formul:ticolor development and the photosensitive material. passing theassembly through an exposure zone to effect the exposure of thephotosensitive material and then passing the same through a heating zoneto effect the heat transfer of the coupler (a).

Since the color former of this invention contains a thermosublimative,organic. solid transfer promoter as well as the coupler (a). in the heattransfer of the coupler (a) the heat transfer temperature can beconsiderably lowered by the interaction of the coupler (a) and thetransfer promoter, as compared with the case where thecoupler (a) isused singly. Further, when a plurality of couplers (a), (a'). (a)forming colors differing in hues are coated on predetermined portions ofan original to be copied and the heat transfer is conducted, the heattransfer temperatures of couplers (a). (a'). (a") can be approximatedbecause of the presence of the thermosublimative, organic. solidtransfer promotor.

The photosensitive material which has been thus exposed to light and ona predetermined portion of which the coupler (u) has beenheat-transferred, is developed by customary known developing methods.The coupler (b) may be either contained in the photosensitive materialin advance or made present in the developer. The development may beconducted by either a dry method or a wet method. When a photosensitivematerial containing coupler (h) as well as diazonium salt is used. it ispreferred that prior to the development the photosensitive material onwhich the coupler (a) has been heat-transferred is subjected to anaffinity-increasing pre-trcatment with a treating liquor comprising.singly or in combination. an aliphatic alcohol. an aromatic solvent. anester. a glycol or a liquid having OH groups and boiling at 100 200C.such as water or high boiling point alcohols, to thereby attain auniform contact between the heat-transferred coupler (a) and thediazonium salt remaining unexposed. In conducting the abovepre-treatment it is desired to allow the above treating liquor tocontact the photosensitive material while keeping the liquor in theliquid or vapor state. In the case of the dry development. thedevelopment may be accomplished sufficiently only by exposing thelightexposed photosensitive material to a mixture of'ammonia and steam.Whena one-component-type photosen- .12 sitive sheet for wet developmentis used. the development can be accomplished by dipping. roller coatingor spraying methods with useofa liquid developer having. for instance.the following recipe:

Coupler (h) 0.2 5' Alkali 0.5 10C: Reducing agent 0 20 2 Surfactant 00.5 '2 Water balance When a two-component-type photosensitive sheet forwet development is used. the development may be accomplished bycontacting the light-exposed photosensitive sheet with a liquiddeveloper containing an alkali.

Thus multi-colored reproductive copies in which the portioncorresponding to the predetermined portion of the original is coloredwith a dyestuff (a )(c) and other portions are colored with a dyestuff(b)(() can be obtained.

The diazo-type multicolor reproduction process with use of the colorformer of this invention will now be explained by referring to theaccompanying drawings.

FIGS. ,1 and 2 are diagrams illustrating the process for obtaining multicolored copies with use of the color former of this invention.

In the embodiment of this invention illustrated in FIG. 1, differentthermovolatile or thermosublimative couplers 2 and 3 are coated on theback surfaces of images 2 and 3, respectively, of an original havingimages I, 2 and 3. When the so formed original for multicolordevelopment is overlapped on a photosensitive paper, and exposed tolight emitted from a suitable light source. latent images 1, 2" and 3corresponding to images 1, 2 and 3 are formed on the photosensitivelayer and couplers 2 and 3' are transferred on the upper surface of thephotosensitive layer by the heat from the light source. When thisphotosensitive sheet is developed. the diazonium salt in latent images2" and 3 of the photosensitive layer reacts selectively with transferredcouplers 2' and 3. while the diazonium salt in latent image 1" reactswith a coupler contained in the photosensitive layer. As a result areproductive copy which has images ll, 12 and 13 colored in differenthues is obtained.

FIG. 2 is a view illustrating an embodiment similar to the aboveembodiment shown in FIG. 1, except that a heat-transferable sheetcontaining coupler 2 and another heat-transferable sheet containingcoupler 3 are applied to the back surfaces of images 2 and 3,respectively.

When the color former of this invention is used for the multicolorreproduction, it is possible to heat transfer the coupler (a) from thepredetermined portion of the original to be copied in a different hue tothe photosensitive material at a relatively low temperature, i.e., atemperature only l0 20C. higher than the temperature adopted in theordinary diazo-type reproduction process. and therefore. it is possibleto obtain a copy in which the portion corresponding to the predeterminedportion of the original is colored selectively in a different hue verydistinctly without substantial mingling of colors. Further. formation ofa plurality of different colors may be accomplished by one developmenttreatment. Once an original is treated with the color former of thisinvention. at leastSimulti-colored copies, usually 20 I00 multi-col'oredcopies. can be obtained from the original. and it is unnecessary totreat the original repeatedly every time one copy is formed. Further.the treated original used for the multicolor reproduction can bereturned to the original state only by peeling off the layer or sheet ofthe color former applied thereto or by heating the color former-coloredoriginal at about 100C.

The multicolor reproduction process with use of the color former of thisinvention is effectively and conveniently applied when copies in whichspecial portions are colored in different hues are desired, and further.ordinary multi-colored copies can be obtained with ease in accordancewith this invention.

This invention will now be explained by referring to examples.

Examples of Preparation of lnklike Color Former Composition for Use inMulticolor Reproduction:

EXAMPLE 1 An ink-like composition of the following recipe is prepared asa yellow color-forming agent for treating the back surface of anoriginal:

Acetoacetic anilide 20 i Alkyd resin 3 g Camphor l5 g Diethylcne glycol5 g Tolyol balance Total 100 ml The above composition is directly usedas a material to be coated on the back surface of a portion of theoriginal desired to be reproduced in yellow by means of a brush. acoating roller or a sprayer. or after it has been charged in a felt penor a ball pen. it is used as a material for treating the back surface ofa portion of the original desired to be reproduced in yellow.

EXAMPLE 2 An ink-like composition for forming a yellowish orange coloris prepared by using acetoacetic-ochloroanilide instead of theacetoacetic anilide of Example 1.

EXAMPLE 3 An ink-like composition of the following recipe is prepared asa red color-forming agent for treating the back surface of an original:

l-Phenyl-3-mcthylpyrazolone (5) 25 i g l-lydrochloric acid (36 a l 5 mlNaphthalene l5 g (ilyeerinc g Ethanol balance Total 100 ml The abovecomposition is directly used as a material to be coated on the backsurface of a portion of the original to be reproduced in red by means ofa brush, a coating roller or a sprayer. or after it has been charged ina felt pen or a ball pen. it is used as a material for treating the backsurface of a portion of the original to be reproduced in red.

EXAMPLE 4 An ink-like composition of the following recipe is prepared asa brown color-forming agent for treating the back surface of anoriginal:

Resorcin 20 g \inyl acetate resin 3 g ()xalic acid' l5 g Methanol 0 mlWater balance Total ltltl ml The above composition is directly used as amaterial to be coated on the back surface of a portion of the originaldesired to be reproduced in brown by means of a brush. a coating rolleror a sprayer. or after it has been charged in a felt pen or a ball pen.it is used as a material for treating the back surface of a portion ofthe original desired to be reproduced in brown.

EXAMPLE 5 An ink-like composition of the following recipe is prepared asa blue color forming agent for treating the back surface of an original:

2.3-Dihydroxynaphthalenc g Alkyd resin 3 g Bornane l5 g Ethylene glycoll() g l-Ithanol balance Total ltltl ml The above composition is directlyused as a material to be coated on the back surface of a portion of theoriginal desired to be reproduced in blue by means of a brush. a coatingroller or a sprayer. or after it has been charged in a felt pen or aball pen. it is used as a color former for treating the back surface ofa portion of the original to be reproduced in blue.

EXAMPLE 6 An ink-like composition of the following recipe is prepared areddish brown color-forming agent for treating the back surface of theoriginal:

Dimcthyl-m-aminophcnol 20 g Naphthalene l5 g Glycerine It) g Ethanolbalance Total I00 ml EXAMPLE 7 A waxy composition to be used as a yellowcolorforming agent for treating the back surface of an original .isprepared by heat melting Acetoacetic acid anilide g Camphor 15 g Stearicacid l()() g Paraffin g Terraabla and solidifying the melt.

The above composition is molded into a crayon sticklike or chalk-likeform and is used as a color former to be coated on the back surface of aportion of the original desired to be reproduced in yellow.

EXAMPLE 8 A waxy composition to be used as a yellowish browncolor-forming agent is prepared by heat melting Pyrogallol 20 g Menthol15 g Paraffin 50 g Terra abla 70 g HLIZC was 20 g Stearic acid 100 gMagnesium carbonate 20 g and solidifying the melt.

The so formed composition is molded into a crayon stick-like orchalk-like form and is used as a material for coating the back surfaceof a portion of an original desired to be reproduced in a different hue.

EXAMPLE 9 To the composition of Example 8 100 g of mineral oil and 30 gof oleic acid are added, and the mixture is kneaded in a ball mill.Then, the kneaded mixture is coated on a substrate such as paper toobtain a pressure-sensitive copy sheet. The so formed copy sheet isoverlapped on the back surface of an original and the pressing iseffected thereon by means ofa typewriter or other writing tool. Thus.the sheet is used as a material for forming a layer of the waxy colorformer agent on the back surface of a portion of the original desired tobe reproduced in a different hue.

EXAMPLE 10 A waxy composition for forming a red color is prepared byheat melting l-Phenyl-3-methylpyrazolonc 25 g p-Diehlorohcnzenc l5 gParaffin 50 g Stearic acid 100 g Diatomeceous earth 3() g Haze wax 20 gand solidifying the melt.

The above composition is molded into a crayon sticklike or chalk-likeform and is used as a material for coating the back surface of a portionof the original desired to be reproduced in a different hue.

EXAMPLE ll To the composition of Example 100 g of mineral oil. 50 goleic acid and g of Permanent Red are added. and the mixture is kneadedin a ball mill to dispcrse additional components uniformly. Then. thekneaded mixture is coated on a substrate as paper to obtain apressure-sensitive copy sheet. The so formed pressure-sensitive copysheet is used as a material for forming a layer of the waxy color formercomposition 6 on the back surface of a portion of the original to becopied in a different hue. in the same manner as described in Example 9.

EXAMPLE l2 7 A waxy color former composition for forming a blue color isprepared by heat melting 2.3-Dihydroxynaphthalenc 30 g Naphthalene 15 gStearic acid g Paraffin 50 g Diatomaeeous earth 30 g Haze wax 20 g andsolidifying the melt.

The above composition is molded into a crayon sticklike form and is usedas a material to be coated on the back surface of a portion of theoriginal desired to be reproduced into a different hue.

EXAMPLE 13 To the composition of Example 12 lOO g of mineral oil, 30 gof oleic acid, 20 g ofOil Blue and 50 ml of ethanol are added. Themixture is well kneaded in a ball mill and coated on a substrate such aspaper to form a pressure-sensitive copy sheet. The sheet is used as amaterial for forming a layer of the waxy color former composition on theback surface of the original to be reproduced in a different hue. in thesame manner as described in Example 9.

Examples of Preparation of Coupler-Transferring Sheets Comprising ColorFormer:

EXAMPLE 14 A composition of the following recipe is prepared as a redcolor-forming agent for treating the back surface of an original:

l-Phenyl-3-methylpyrazolone (5) 25 g Camphor l5 g Triacetatc resin l0 gMethanol 50 ml Acetone 50 ml .The above composition is coated on atransparent or semi-transparent sheet such as polyester film by means'of a rod coater and dried at a relatively low temperature (40 50C.) toform a sheet for heat-transferring the coupler. After being cut into adesired size according to need. the sheet is used as a material to beapplied to the back surface ofa portion of an original desired to bereproduced in a different hue.

EXAMPLE 15 A composition of the following recipe is prepared as a browncolor-forming agent for treating the back surface of an original:

m-Aminophenol 25 g Anthranic acid l5 g Triaeetate resin 10 g Methanol 50ml Acetone 50 ml The above composition is coated on a transparent orsemi-transparent sheet such as polyester film by means of a rod coaterand dried at a relatively low temperature (40 50C.) to form a sheet forheat-transferring the coupler. After being cut into a desired sizeaccording to need, the sheet is used as a material to be applied to theback surface of a portion of the original desired to be reproduced in adifferent hue.

EXAMPLE 16 A composition to be used as a brown color-forming agent fortreating the back surface of an original is prepared by using pyrogallolinstead of l-phenyl-3- methylpyrazolone (5) in Example l4. From thiscomposition a sheet is formed for heat-transferring the coupler capableof forming a brown color.

EXAMPLE 17 A composition to be used as a blue color-forming agent fortreating the back surface of an original is prepared by using1,6-dihydroxynaphthalene instead of l-phenyl-3-methylpyrazolone inExample 14. From this composition a sheet is prepared for heattransferring the coupler capable of forming a blue color.

Application of Color-Forming Agents to Diazo-type MulticolorReproduction:

EXAMPLE 18 Multicolor-forming diazo-type photosensitive paper in use forwet development First, l g of 4-diazo-2,5-diethoxy-benzoylanilinechloride l/2ZnCl 8 g of citric acid, 0.1 g of Patent Blue and 10 g ofdextrin are dissolved successively in water, and the amount of thesolution is adjusted to 1 liter by controlling the amount of wateradded. The so formed solution is coated on a base paper of aphotosensitive sheet by a customary coating method employing an airknife coater, and dried to form a photosensitive sheet.

The sheet is overlapped on an original in which the back surface of aportion is treated with the ink-like color former composition preparedin Example 1 and the back surface of another portion is treated with thecolor former composition prepared in Example 3. Then the assembly isheated and light exposed by means of a mercury lamp and developed with aliquid developer of the following recipe:

NW acid Potassium carbonate Sodium bicarbonate Sodium thiosull'ateActivator Water b Aurora Total 1 EXAMPLE l9 Multicolor-Forming DiazotypePhotosensitive Sheet for Dry Development A solution of the followingrecipe is prepared:

4-DiazoN-ethyl-N-/3-hydroxycth)laniline -Continued chloride l/ZZnCl gDiethylene glycol 50 g Citric acid 20 g Bisl 5-hydrosy-7-sull'onaphthyll2 llaminc 15 g Zinc chloride 40 g Thiourea g Patent Blue (Ll g Waterbalance 'lotal l liter The solution is coated on a base paper by acustomary coating procedure such as using an air knife coater and driedto form a photosensitive sheet.

The sheet is piled on an original in which one portion of the backsurface is treated with the color former composition prepared in Example2, another portion of the back surface is treated with the color formercomposition prepared in Example 3 and still another portion of the backsurface is treated with the color former composition of Example 5. Then,the assembly is heated and exposed to light by means of a mercury lampto form a latent image of the diazonium salt.

Next, the so treated sheet is subjected to development with gasifiedammonia and steam. Thus. there is obtained as a result a clearmulticolor copy in which a portion corresponding to the portion treatedwith the material of Example 2 is colored in yellowish orange, a portioncorresponding to the portion treated with the material of Example 3 iscolored in reddish brown, a portion corresponding to the material ofExample 5 is colored in bluish violet, and a portion corresponding tothe untreated portion of the original is colored in dark blue isobtained.

EXAMPLE 20 Multicolor-forming diazo'type photosensitive paper in use fordry development A solution of the following recipe is prepared:

4-Diazo-N.N-dimethyl-aniline chloride.l/2Zn(.l 10 g Diethylene glycol 40g Citric acid g 2.3-Dihydroxynaphthalene-f sull'onie acid 20 g Zincchloride 50 g Thiourea 50 g Patent Blue 0.1 g Water balance Total 1liter In the same manner as in Example, 18, a photosensitive paper isprepared from the above solution by coating and drying. Thephotosensitive paper is piled on an original, a portion of the backsurface of which is treated with the coupler-heat-transferring sheetprepared in Example-l4. Then the assembly is heated and printed by meansofa mercury lamp, followed by development with gaseous ammonia andsteam. As a result a clear two-color reproductive copy in which aportion corresponding to the portion treated with the treating agent ofExample l4 is colored in red and another portion corresponding to theuntreated portion is colored in dark blue is obtained.

EXAMPLE 21 Multicolor-forming photosensitive paper in use for drydevelopment A solution of the following recipe is prepared:

4-l)ialo-N.N-dimethylaniline chloride.l/27.nCl g Ethylene glycol 50 gCitric acid 'g 2.7-Dihydroxynaphthalene 3.(i-tlisulfonic acid sodiumsalt I 8 g Zinc chloride 20 g Thiourea H10 gl.3.o-Naphthalene-trisulfonic acid sodium salt 20 g Patent Blue 0.1 gWater balance Total 1 liter By a customary coating method such as usingan air knife coater, a photosensitive paper is prepared from the abovesolution. The photosensitive paper is overlapped on an original in whicha portion of the back surface is treated with the waxy compositionprepared in Example 8 and another portion of the back surface is treatedwith the composition prepared in Example 10. The assembly is exposed tolight and heated by means of a mercury lamp. Then, the so treated sheetis subjected to development with gasified ammonia and steam. As a resulta clear three-color reproductive copy in which a portion correspondingto the portion of the original treated with the composition of Example 8is colored in brown, a portion corresponding to the portiontreated withthe composition of Example 10 is colored in red, and other portioncorresponding to the untreated portion of the original is colored inbluish violet is obtained.

EXAMPLE 22 Multicolor-forming photosensitive paper for dry development Asolution of the following recipe is prepared:

4-DiaxoN.N-dicthylaniline The above solution is applied to aphotosensitive paper substrate by a customary coating method such asusing an air knife coater, and the resulting photosensitive sheet ispiled on an original in which the back surface of a part of an image istreated with the ink-like composition obtained 'in-Example 3. the backsurface of another part of the image is treated with the composition ofExample 4 and the back surface of still another part is treated with thecomposition of Example 5. Then, the assembly is heated and printed at 7080C. by means ofa mercury lamp, and the so treated photosensitive sheetis developed with gaseous ammonia and steam. As a result a four-coloredcopy of a clear color contrast is obtained in which a portioncorresponding to the portion treated with the composition of Example 3is colored in red, a portion'corresponding to the portion treated withthe composition of Example 4 is colored in yellowish brown, a portioncorresponding to the Patent Blue portion treated with ithefeoinpositionof Example 5 is colored in blue. and a portion corresponding to theuntreated portion of the original is colored in black.

EXAMPLE 23 Multicolor-forming diazo-type photosensitive paper for drydevelopment for forming second original A solution of the followingrecipe is prepared:

The above solution is coated on a semi-transparent paper for secondoriginal such as tracing paper and dried to form a photosensitive paper.The photosensitive paper is piled on an original, a portion of the backsurface of which is treated with the waxy color former compositionprepared in Example 12. Then the assembly is'heated and printed by meansof a mercury lamp, followed by development with gaseous ammonia andsteam. As a result a clear two-color reproductive copy usable as theintermediate second original is obtained in which a portioncorresponding to the portion of the original treated with thecomposition of Example 12 is colored in red and another portioncorresponding to the untreated portion of the original is colored inyellowish brown.

EXAMPLE 24 MuIti-color-forming photosensitive paper for dry developmentA solution of the following recipe is prepared:

4-DizmrN-ethyl-N-hydroxyethylaniline ehloride.l/2ZnCl 15 g Diethyleneglycol St) g Citric acid 30 g a-resorcylic acid ethanol amine 8 g Zincchloride 50 g Thiourea 25 g Patent Blue 0.] g Water balance Total 1liter By a customary coatingmethod such as using an air knife eoater,the above solution is applied to a substrate of a photosensitivepaperand dried. The so formed photosensitive paper is piled on an original, aportion of the back surface of which is treated with acouplerheat-transferring sheet prepared in Example 17. and the assemblyis heated at 60 C. and printed by means of a mercury lamp, followed bydevelopment with gaseous ammonia and steam. As a result a cleartwo-color reproductive copy without any substantial mingling of colorsis obtained, in which a portion corresponding to the portion oftheoriginal treated with the sheet obtaine d in Example 17 is colored inblue and the remaining portion corresponding to the untreated portion ofthe original is colored inred.

EXAMPLE 2'5 Multicolor-forming sensitive paper in use for either dry orwet development A solution of the following recipe is prepared:

-lDiane-2.5-dibutoxy-N-phenylmorpholinellIZnCl l5 g Citric acid 30 gDiethtlene glycol 40 g [3 Hydroxynaphthonic acid aminoethyl aminelhydroehloridel 7 g 'l'hiourea 40 g Zinc chloride 30 g Patent Blue (Ll gWater balance Total 1 liter From the above solution. a photosensitivepaper is prepared by conducting the coating and drying in the samemanner as in Example 18. The so formed photo sensitive paper is piled onan original. a portion of the back surface of which is treated with thepressuresensitive sheet prepared in Example 9 and another portion of theback surface of which is treated with the pressure-sensitive sheetprepared in Example l 1. Then the assembly is heated and printed bymeans of a mercury lamp. followed by development with gaseous ammoniaand steam or with an alkaline liquid developer of the following recipe:

Potassium carbonate 20 g Sodium thiosullate 40 g Sodium bicarbonate 30 gPotassium tctraborate 5 g Water balance Total 1 liter As a result aclear three-color reproductive copy without any substantial mingling ofcolors is obtained, in which a portion corresponding to the portion ofthe original treated with the pressure-sensitive sheet of Example iscolored in brown, a portion corresponding to the portion of the originaltreated with the pressuresensitive sheet of Example 1 l is coloredin'red and the remaining portion corresponding to the untreated portionof the original is colored in blue.

EXAMPLE 26 Multicolor-forming film A solution of the following recipe isprepared:

4-Diazo-2.5 dibutoxy-N-phenyl morpholinel/ZZnCh [5 g Citric acid gB'Hydroxynaphthoie acid ethanol amine 7 g Triaeetate resin g Oil Blue 02g Acetone 400 ml Methanol 700 ml The solution is coated on a polyesterfilm by a rod coater and dried at a relatively low temperature (40 50C.)by warm air to form a photosensitive film. The film is piled on anoriginal in which a part of the back surface of an original imagcistreated with the colorforming agent prepared in Example 3 and anotherpart ofthe back surface ofthe original image is treated with thecolor-forming agent prepared in Example 4. The

assembly is exposed to light by a mercury lamp and heated and printed.The photosensitive film containing a latent image of the diazonium saltis developed with gasified ammonium and steam. As a result a clearthree-color reproductive copy without any substantial mingling ofcolors'is obtained. in which a portion corresponding to the part treatedwith the treating material of Example 3 is colored in red. a portioncorresponding to the part treated with the treating material of Example4 is colored in brown. and another portion corresponding to theuntreated part ofthe original is colored in blue.

COMPARATIVE EXAMPLE 1 This example illustrates results of comparativeexperiments conducted to confirm effects attained by the in corporationof the thermosublimative. organic, solid transfer promotor in the colorformer of this invention.

EXPERIMENTAL PROCEDURES Four ink-like color-forming compositions of thefollowing recipes are prepared.

Each of the above solutions is coated on the back surface of asemi-transparent original (tracing paper; Chemical No. 60) in an amountof about 0.2 g/m". The so coated original is dried to form a samplesheet original. Then, the sample sheet is piled on the photosensitivesheet prepared in Example 21 in a manner such that the treated surfaceof the sample is in face-toface contact with the photosensitive layer ofthe photosensitive sheet. Then, the assembly is allowed to pass throughhot rolls maintained at 50C.. 60C.. C.. C. and C., respectively, toeffect the heat transfer of the thermovolatile or thermosublimativecoupler. Then, the so treated photosensitive sheet is subjected to thedevelopment with gaseous ammonia and steam. With respect to each sampleoriginal, the number of copies ofa distinct color contrast obtained ateach heat transfer temperature is counted. Results are shown in Table 1below.

Table 1 Recipe No. 50 60 70 80 90 Table l-Continued Number of Copies ofDistinct Color Contrast Heat Transfer Temperature (C.) 1

Recipe No. 50 60 80 90 COMPARATIVE EXAMPLE 2 EXPERIMENT PROCEDURES Asthe thermovolatile or thermosublimative coupler sample1-phenyl-3-methylpyrazolone (5) and resorcin are selectedEach of thesample chemicals is sufficiently ground in a mortar and is sufficientlydried in a silica gel desiccator. A precisely weighed amount (0.3 g) ofeach sample is charged in a vessel having a certain inner surface areaand subjected to a heat treatment at 100C., 1 C. and 120C. The weight ofthe sample is determined at certain time intervals and the weight lossis calculated each time.

Then, each sample is blended with 1.5 g of camphor (special grade) andthe blend is sufficiently mixed and ground in a mortar. Then, the blendis subjected to the same heat treatment as above to determine the weightloss of the blend. Then, the weight loss of the coupler alone iscalculated by reducing the weight loss of camphor alone determinedseparately, from the above determined weight loss of the blend. Thus,the effect of camphor for promoting the volatilization or sublimation ofthe sample coupler is examined. Results are shown in Tables 2 and 3below.

Table 2 Weight Loss (mg) of l-Phenyl-3-Methylpyraznlone (5) TreatmentTime Treatment Temperature In Tables 2 and 3. the values are values 1nparenthesis obtained when d-camphor is incorporated in the samplecoupler.

From the results of Comparative Examples 1 and 2. the following can beconcluded.

As is seen from the results shown in Table l, the use of the colorformer of this invention increases the number of copies by 7 sheets atC.. by 12 sheets at C. and by 18 sheets at C. in the case of l-phenyl-3-methylpyrazolone (5). as compared with the use of the coupler alone.Accordingly. it is construed that the heat transfer temperature may belowered by about 10 15C. with the use of the color former of thisinvention comprising the thermovolatile or thermosublimative coupler andthe thermosublimative. organic. solid transfer promotor. 1n the case ofresorcin. the use of the color former of this invention increases thenumber of copies by 7 sheets at 60C. and by 22 sheets at 70C.Accordingly. it is construed that also in this case the heat transfertemperature may be lowered by about 10 15C. with the use of the colorformer of this invention.

As is seen from the results of Comparative Example 2 shown in Tables 2and 3, when comparison is made at the same treatment temperature. in thecase of the color former of this invention the weight loss ofl-phenyl-3-methylpyrazolone (5) is about 2.5 times as large as in thecase of the color former free of camphor, and the weight loss ofresorcin in the case of the color former of this invention is about 2times as large as in the case of the color former comprising resorcinalone. Accordingly, it is construed that the heat transfer temperaturemay be lowered by about 10 15C. with the use of the color former of thisinvention.

In view of the foregoing, it can be readily understood that when thethermosublimative. organic, solid transfer promotor is used incombination with a thermovolatile or thermosublimative coupler. theefficiency of transfer of the coupler can be greatly improved.

What we claim is:

l. A waxy color former composition of crayon sticklike form or achalk-like form for treating the back surface of an original indiazo-type multicolor reproduction, which consists essentially of a. athermovolatile or thermosublimable azo coupler;

and

b. a solid organic thermosublimable compound selected from the groupconsisting of camphor. naphthalene. bornane. menthol. andp-dichlorobenzene.

said components (a) and (b) dispersed in a wax.

2. The waxy color former composition of claim 1, in which saidcomposition consists essentially of a. 0.540.0% by weight of athermovolatile or thermosublimable azo coupler;

1). 05-25% by weight of a solid organic thermosublimable compoundselected from the group consisting of camphor. naphthalene. bornane.menthol. and p-dichlorobenzene c. 80-571 by weight of a wax; and

d. ()10% by weight of color material.

3. The waxy color former composition of claim 1 in which saidthermovolatile or thermosublimable azo coupler is at least one memberselected from the group consisting of phenol compounds.hydroxynaphthalene compounds. aniline compounds and active methylenegroup-containing compoundsv 4. The waxy color former composition ofclaim 1 in which said composition consists essentially of;

Acetoacetic acid aniline 15 parts by weight. ('amphor l parts by weight.Slearie acid H parts by weight. Paral'l'in 50 parts by weight.

and Terra abla 50 parts by weight.

5. The waxy color former composition of claim 1 in which saidcomposition consists essentially of:

Pyrogallol 21) parts by weight. Menthol parts by weight. Paraffin 50parts by weight. Terra abla 7!) parts by weight. Haze wax parts byweight. Stearic acid [00 parts by weight.

and Magnesium carbonate 20 parts by weight.

6. The waxy color former composition of claim 1 in which saidcomposition consists essentially of:

l-Phenyl-B-methyl pyrazolone parts by weight.

p-Dichlorobenzene 12 parts by weight.

Paraffin 50 parts by weight.

Stearic acid 100 parts by weight.

Diatomaceous earth parts by weight.

and

Have wax 20 parts by weight.

7. The waxy color former composition of'claim l in which saidcomposition consists essentially of:

2.3-dihydroxynaphthalene 30 parts by weight.

Naphthalene 15 parts hyweight.

Stearic acid IOU parts by weight.

Paraffin parts by weight.

Diatomaccous earth 3() parts by weight.

and

Have wax 20 parts by weight.

pound (h) is bornane.

11. The waxy color former composition of claim 1 wherein said solidorganic thermosublimable compound (b) is menthol.

12. The waxy color former composition of claim 1 wherein said solidorganic thermosublimable compound (h) is p-dichlorobenzene.

13. An ink-like color former composition for treating the back surfaceof an original in the diazo-type multicolor reproduction. which consistsessentially of a. 5.040.()'/( by weight of a thermovolatile orthermosublimable azo coupler;

b. 5.040.071 by weight ofa solid organic thermosublimable compoundselected from the group consisting of camphor. naphthalene. bornane.menthol. and p-dichlorobenzene;

c. ()-().3'/( by weight of a color material: and

d. 0-5.07: by weight of a resinous binder. said components (a). (b). (c)and (d) dispersed in a dispersion medium selected from aliphaticalcohols. aromatic solvents and neutral liquids containing OH groups.said dispersion medium boiling at l ()()-250C 14. The ink-like colorformer composition of claim 13 wherein said solid organicthermosublimable compound (b) is camphor.

15. The ink-like color former composition of claim 13 wherein said solidorganic thermosublimable compound (b) is naphthalene.

16. The ink-like color former composition of claim 13 wherein said solidorganic thermosublimable compound (b) is bornane.

17. The ink-like color former composition of claim 13 wherein said solidorganic thermosublimable compound (h) is menthol.

18. The ink-like color former composition of claim 13 wherein said solidorganic thermosublimahle compound (b) is p-dichlorobenzene.

19. The ink-like color former composition of claim 13 in which saidthermovolatile or thermosublimable azo coupler is at least one memberselected from the group consisting ofphcnol compounds.hydroxynaphthalene compounds. aniline compounds. and active methylenegroup-containing compounds.

1. A WAXY COLOR FORMER COMPOSITION OF CRAYON STICK-LIKE FORM OR ACHALK-LIKE FORM FOR TREATING THE BACK SURFACE OF AN ORIGINAL INDIAZO-TYPE MULTICOLOR REPRODUCTION, WHICH CONSISTS ESSENTIALLY OF A. ATHERMOVOLATILE OR THERMOSUBLIMABLE AZO COUPLER, AND B. A SOLID ORGANICTHERMOSUBLIMABLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF CAMPHOR,NAPHTHALENE, BORNANE, MENTHOL, AND P-DICHLOROBENZENE, SAID COMPONENTS(A) AND (B) DISPERSED IN A WAX.
 2. The waxy color former composition ofclaim 1, in which said composition consists essentially of a. 0.5-40.0%by weight of a thermovolatile or thermosublimable azo coupler; b.0.5-25% by weight of a solid organic thermosublimable compound selectedfrom the group consisting of camphor, naphthalene, bornane, menthol, andp-dichlorobenzene,; c. 80-5% by weight of a wax; and d. 0-10% by weightof color material.
 3. The waxy color former composition of claim 1 inwhich said thermovolatile or thermosublimable azo coupler is at leastone member selected from the group consisting of phenol compounds,hydroxynaphthalene compounds, aniline compounds and active methylenegroup-containing compounds.
 4. The waxy color former composition ofclaim 1 in which said composition consists essentially of:
 5. The waxycolor former composition of claim 1 in which said composition consistsessentially of:
 6. The waxy color former composition of claim 1 in whichsaid composition consists essentially of:
 7. The waxy color formercomposition of claim 1 in which said composition consists essentiallyof:
 8. The waxy color former composition of claim 1 wherein said solidorganic thermosublimable compound (b) is camphor.
 9. The waxy colorformer composition of claim 1 wherein said solid organicthermosublimable compound (b) is naphthalene.
 10. The waxy color formercomposition of claim 1 wherein said solid organic thermosublimablecompound (b) is bornane.
 11. The waxy color former composition of claim1 wherein said solid organic thermosublimable compound (b) is menthol.12. The waxy color former composition of claim 1 wherein said solidorganic thermosublimable compound (b) is p-dichlorobenzene.
 13. ANINK-LIKE COLOR FORMER COMPOSITION FOR TREATING THE BACK SURFACE OF ANORIGINAL IN THE DIAZO-TYPE MULTICOLOR REPRODUCTION, WHICH CONSISTSESSENTIALLY OF A. 5.0-40.0% BY WEIGHT OF A THERMOVALTILE ORTHERMOSUBLIMABLE AZO COUPLER, B. 5.0-30.0% BY WEIGHT OF A SOLID ORGANICTHERMOSUBLIMABLE COMPOUND SELECTED FROM THE GROUP CONSISTING OF CAMPHOR,NAPHTHALENE, BORNANE, METHOL, AND P-DICHLOROBENZENE, C. 0-0.3% BY WEIGHTOF A COLOR MATERIAL, AND D. 0-5.0% BY WEIGHT OF A RESINOUS BINDER, SAIDCOMPONENTS (A), (B), (C) AND (D) DISPERSED IN A DISPERSION MEDIUMSELECTED FROM ALIPHATIC ALCOHOLS, AROMATIC SOLVENTS AND NEUTRAL LIQUIDSCONTAINING OH GROUPS, SAID DISPERSION MEDIUM BOILING AT 100*-250*C. 14.The ink-like color former composition of claim 13 wherein said solidorganic thermosublimable compound (b) is camphor.
 15. The ink-like colorformer composition of claim 13 wherein said solid organicthermosublimable compound (b) is naphthalene.
 16. The ink-like colorformer composition of claim 13 wherein said solid organicthermosublimable compound (b) is bornane.
 17. The ink-like color formercomposition of claim 13 wherein said solid organic thermosublimablecompound (b) is menthol.
 18. The ink-like color former composition ofclaim 13 wherein said solid organic thermosublimable compound (b) isp-dichlorobenzene.
 19. The ink-like color former composition of claim 13in which said thermovolatile or thermosublimable azo coupler is at leastone member selected from the group consisting of phenol compounds,hydroxynaphthalene compounds, aniline compounds, and active methylenegroup-containing compounds.